JPS61502402A - Sensitization method for oxidation/reduction photoreaction catalyst and photoreaction catalyst - Google Patents

Sensitization method for oxidation/reduction photoreaction catalyst and photoreaction catalyst

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JPS61502402A
JPS61502402A JP60501479A JP50147985A JPS61502402A JP S61502402 A JPS61502402 A JP S61502402A JP 60501479 A JP60501479 A JP 60501479A JP 50147985 A JP50147985 A JP 50147985A JP S61502402 A JPS61502402 A JP S61502402A
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グレーツエル　ミカエル
ゼルポーネ　ニツク
デユオンホン　デユン
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エル　エ−　シユテイツフツング
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    • C09K9/02—Organic tenebrescent materials
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J23/462—Ruthenium
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    • C01B3/042—Decomposition of water
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    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

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Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 酸化／還元光反応触媒の増感方法および光反応触媒 この発明は半導体系酸化／還元光反応触媒の増感方法、これによって得られた光 反応触媒及び可視光線中の水性又は水性有機液体の光酸化若しくは水性液体の光 分解用の上記光反応触媒の利用に関する。[Detailed description of the invention] Sensitization method for oxidation/reduction photoreaction catalyst and photoreaction catalyst This invention describes a method for sensitizing semiconductor-based oxidation/reduction photocatalysts, and the light obtained by this method. Photo-oxidation of reaction catalysts and aqueous or aqueous organic liquids in visible light or light of aqueous liquids The present invention relates to the use of the above photoreaction catalyst for decomposition.

その目的のひとつは水素の光反応による製造である。One of its purposes is the production of hydrogen by photoreaction.

この発明の主題は請求の範囲に記載されている。The subject matter of the invention is defined in the claims.

光電気化学セル若しくは水素の光化学発生器、特に太陽エネルギー変換に基づく 装置で遭遇する当面の問題は、このエネルギー変換の効率である。この問題を克 服するため現在、光反応染料による光反応触媒表面の改質、上記光反応触媒の適 当な物質によるドーピングなど、さまざまな解決方法が提案されている。Photoelectrochemical cells or photochemical generators of hydrogen, especially based on solar energy conversion The immediate problem encountered with the device is the efficiency of this energy conversion. overcome this problem Currently, in order to meet the requirements of Various solutions have been proposed, including doping with suitable substances.

水性液体の光分解などの用途で太陽エネルギー変換効率の問題を解決するため、 可視光線領域内若しくはその近傍に光吸収帯域を有する光反応触媒に着目するこ とは興味深い。チタニウムと８−ヒドロキシキノリンの錯塩を使用して酸化チタ ン（ＴｉＯ２）の錯塩を形成し、酸化チタン粒子を可視光線中で利用できるよう にこれら粒子を増感できる〔これに関連する。　Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、 　１０５　、５６９５（１９８３）参照〕。To solve the problem of solar energy conversion efficiency in applications such as photolysis of aqueous liquids, Focusing on photoreaction catalysts that have a light absorption band within or near the visible light range. That's interesting. Titanium oxide using a complex salt of titanium and 8-hydroxyquinoline Forms a complex salt of titanium oxide (TiO2) and makes titanium oxide particles available in visible light. These particles can be sensitized to [related to this]. J, Am, Chem, Soc, 105, 5695 (1983)].

しかしこの種類の光反応触媒の利用は、水の光分解により酸素を製造できないと いうことにより制約される。However, the use of this type of photocatalyst requires that oxygen cannot be produced by photolysis of water. It is limited by what you say.

この発明の目的は、可視光線中で水性液体を光分解して、満足できる効率で、水 素と酸素の発生を可能にする増感光反応触媒を提供するにある。これは請求範囲 に示した方法により、半導体系酸化／還元光触媒を増感することにより得られる 。It is an object of this invention to photolyze aqueous liquids in visible light to produce water with satisfactory efficiency. The object of the present invention is to provide a sensitized photoreaction catalyst that enables the generation of hydrogen and oxygen. This is the scope of claim Obtained by sensitizing a semiconductor-based oxidation/reduction photocatalyst using the method shown in .

驚ろくべきことに、酸化チタンなどの半導体系酸化／還元光触媒の表面に例えば ビピリジル若しくはフェナンスロイルタイプの配位子と遷移金属との錯塩の一部 からなるクロモフォール（Ｃｈｒｏｍｏｐｈｏｒｅ）を固定することにより所望 の効果が得られることが見出された。Surprisingly, on the surface of semiconductor-based oxidation/reduction photocatalysts such as titanium oxide, for example, Some complex salts of bipyridyl or phenanthroyl type ligands and transition metals By immobilizing Chromophore consisting of It was found that the following effects can be obtained.

この発明によると、最も一般的にはルテニウム。According to this invention, most commonly ruthenium.

クローム若しくは鉄錯塩の一部がら成り、一般式たゾし、記号りは配位子である ジイソプロピル２．ｆｆ−ビピリジル−４，４′−ジカルボキシレートを表わし 、この錯塩フラグメントから構成されるのが好ましい。It consists of a part of chromium or iron complex salt, the general formula is tazo, and the symbol is a ligand. Diisopropyl2. ff-bipyridyl-4,4'-dicarboxylate , is preferably composed of this complex salt fragment.

このタイプのクロモフォールは光反応触媒の使用状態で完全に安定であり、光反 応触媒の光吸収をシフトさせて６００ｎ’ｍを越える範囲にまで拡大した。This type of chromophol is completely stable under conditions of use as a photocatalyst; The light absorption of the reaction catalyst was shifted to extend beyond 600 nm.

か＼るクロモフォールの安定性は錯塩フラグメントＲｕＬ′＋＋ のチタン酸化物粒子表面への化学的な固定、より正確には以下に示す： （Ｌ＝ニジイソプロピル、２′−ビピリジル−４，４′−ジカルボキシレート〕 のＲｕ　−０−Ｔｉ結合の形成により説明できる。The stability of chromofol is determined by the complex salt fragment RuL'++ chemical fixation on the surface of titanium oxide particles, more precisely: (L=nidiisopropyl, 2'-bipyridyl-4,4'-dicarboxylate) This can be explained by the formation of a Ru-0-Ti bond.

このようにして増感された光反応触媒は、水性若しくは水性有機液体に５９０乃 至６６５ｎｍの波長で光線を照射して、満足すべき効率で水素の入手を可能にす ることが分った。それぞれ水素と酸素を与える水の光分解も同じく効率よく行な われるようになった。The photoreaction catalyst sensitized in this way can be added to an aqueous or aqueous organic liquid at a temperature of 590°C. Irradiation with light at wavelengths up to 665 nm makes it possible to obtain hydrogen with satisfactory efficiency. It turns out that Photolysis of water, which yields hydrogen and oxygen, respectively, is also carried out efficiently. It started to get worse.

この発明によると、光反応触媒は任意の適当な方法によって、半導体の表面に選 択されたタロモフォールを固定することにより増感される。この発明）こよる方 法のひとつの望ましい実施方法では、光反応触媒は、一般式 ％式％ たゾし、Ｌは上記の通りで、Ｘはたとえば塩素などのハロゲン原子を表わし、こ の錯塩の酸性水溶液の存在下で光線照射される。According to the invention, the photoreaction catalyst is selected on the surface of the semiconductor by any suitable method. Sensitization is achieved by immobilizing selected talomofol. This invention) In one preferred implementation of the method, the photoreaction catalyst has the general formula %formula% , L is as above, and X represents a halogen atom such as chlorine; is irradiated with light in the presence of an acidic aqueous solution of the complex salt.

Ｔｉｅ、系の酸化／還元触媒は文献に説明された方法で有利に調製できる。上述 の錯塩の溶液は市販品力）ら入手できる′。Tie-based oxidation/reduction catalysts can be advantageously prepared by methods described in the literature. mentioned above A solution of the complex salt of is available commercially.

光照射のため、選択された量の触媒が、錯塩のそれぞれの場合に応じて０，５乃 至５Ｘ１０−’モル程度の稀釈水溶液中に懸濁される。もし必要であれば、酸を 添加して一般に１−３の範囲の規定値に溶液の２口が調整される。この方法は約 １．５　Ｘ　１０−’モルの錯塩濃度で約２のｐＨ値で実施されるのが好まし７ い。実際の光照射前に、設備はたとえばアルゴンなどの不活性ガスでガス抜きさ れる。このようにして調製された懸濁液が選択された温度、ごく一般的には５０ ℃と沸点との間の賜度に加熱される。操作温度は約１００℃が好ましい。光照射 は研究室で一般に慣用される紫外線（［１”ｙＪ：ｒなど通常の手段で実施され る。照射は実際上、最初に溶解された錯塩がすべて消失するまで、一般に２４時 間以上継絖される。For photoirradiation, the selected amount of catalyst is 0.5 to Suspended in a dilute aqueous solution on the order of 5 x 10-' molar. If necessary, add acid Two portions of the solution are adjusted to a specified value, generally in the range of 1-3, by addition. This method is about It is preferably carried out at a pH value of about 2 with a complex salt concentration of 1.5 x 10-' molar. stomach. Before the actual light irradiation, the equipment is degassed with an inert gas, e.g. argon. It will be done. The suspension thus prepared is heated to a selected temperature, most commonly 50°C. It is heated to a temperature between °C and the boiling point. The operating temperature is preferably about 100°C. light irradiation is carried out by the usual means commonly used in laboratories, such as ultraviolet light ([1”yJ:r). Ru. Irradiation is generally carried out for 24 hours until all initially dissolved complex salts have disappeared. It is connected for more than a while.

このようにして増感された光反応触媒が例えば濾過若しくは超遠心分ｍなどの方 法で捕集し、精製され、最後に従来の方法で乾燥される。経験によるとこのタイ プの光酸化触媒は数週間も使用状態で安定して効果を発揮する。The photoreaction catalyst sensitized in this way can be used, for example, by filtration or ultracentrifugation. It is collected by a method, purified and finally dried by a conventional method. According to experience this Thailand The photo-oxidation catalyst in the photooxidation catalyst remains stable and effective for several weeks.

この発明によると、このタイプの増感光反応触媒は可視光線中で水性液体を照射 することにより水素ガスの発生に有利に利用できる。これは、例えばトリエタノ ールアミンの稀釈水溶液などの水性有機液体の光酸化を実施することにより行な われ、例えば、この有機化合物は電子を放出するドナーのような作用を示す。According to this invention, this type of sensitized photocatalyst irradiates an aqueous liquid in visible light. By doing so, it can be advantageously used to generate hydrogen gas. This is for example trietano This is done by carrying out photooxidation of an aqueous organic liquid, such as a dilute aqueous solution of amine. For example, this organic compound acts like a donor that releases electrons.

このタイプの触媒はそれぞれ酸素と水素を与えるため可視光線中で照射して、例 えば蒸溜水など水性液体の光分解に有利に利用できる。This type of catalyst can be irradiated in visible light to give oxygen and hydrogen respectively, e.g. For example, it can be advantageously used for photolysis of aqueous liquids such as distilled water.

上述の場合に、照射は４００１ｍより大きい、例えば４５０　ｎ　ｍ　、　５０ ０　ｎ　ｍあるいはそれ以上のオーダの波長の光を利用して有利に行なえる。さ らに上記の照射は最も一般的には例えば光反応触媒の増感に使用されるのと同様 な設備中で、選択された水性液体の沸点で行なわれる。In the above case, the irradiation is greater than 4001 m, e.g. 450 nm, 50 nm This can be advantageously carried out using light having a wavelength on the order of 0 nm or more. difference Moreover, the above-mentioned irradiations are most commonly used for example in the sensitization of photocatalysts. The process is carried out in suitable equipment at the boiling point of the selected aqueous liquid.

以下の実施例はこの発明を実施するいくつかの方法の詳細を説明している。これ ら実施例はいかなる実施例１ 酸化チタン系酸化／還元触媒の増感 ａ）触媒の調製　（Ｔ　ｉＯ，／Ｐ　ｔ／Ｒｕｂ、）出発材料ニ ー（ＲｕＬΩＣａｌ、（Ｌ＝ニジインプロピル、２′−ビピリジル−４，４′− ジカルボキシレート）　、　Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ。The following examples provide details of several ways to practice the invention. this Example 1 Sensitization of titanium oxide based oxidation/reduction catalysts a) Preparation of catalyst (TiO,/Pt/Rub,) starting materials -(RuLΩCal, (L=nidiumpropyl, 2'-bipyridyl-4,4'- dicarboxylate), J, Am, Chem, Soc.

υ１，５６９５（１９８３月こより調製−Ｔｉｅ、（アナターゼ、　Ｎｂ含有量 約６００　ｐｐｍ。υ1,5695 (prepared from March 1983 - Tie, (anatase, Nb content Approximately 600 ppm.

主結晶サイズ１００Ａ、　ＢＥＴ　１４５　ｄ／ｆ）−ＴｉＣ１，、Ｊ、Ａｍ、 Ｃｈｅｍ、Ｓｏｃ、　１０５．　６５４７（１９８３）により真空蒸溜により精 製 第一ステップはドーピングレベルで０．１％（７）Ｎｂを与えるため、計算され た所定量のＮｂＣ１，の存在下に、０℃の水中で、一定量のＴ　ｉ　Ｃｌ、を加 水分解することであった。加水分解された溶液（ｐｆ（０，５）はｐＨが２に達 するまで透析された。Main crystal size 100A, BET 145 d/f)-TiC1,, J, Am, Chem, Soc, 105. Purified by vacuum distillation according to 6547 (1983) made The first step is calculated to give a doping level of 0.1%(7)Nb. In the presence of a predetermined amount of NbCl, in water at 0°C, a certain amount of TiCl was added. It was to decompose water. The hydrolyzed solution (pf(0,5) reaches pH 2. Dialysis was performed until

次にＨ，ＰｔＣ１，とＲｕｂ４がこのようにして調製された酸性溶液にそれぞれ 添加され、添加量はＴｉｅ、粒子にそれぞれＰｔおよびＲｕｂ、　０．５％の含 有量を与えるよう算定される。得られた溶液を続いて６０℃で乾固し、残留物が この温度に２４時間保持された。この操作段階で、Ｒｕｂ、のＲｕ０ｔへの瞬間 的な分解が観察された（黒色の沈澱物〕。Next, H, PtC1, and Rub4 were added to the acidic solution prepared in this way, respectively. The added amount is Tie, and the particles contain Pt and Rub, respectively, 0.5%. It is calculated to give a certain amount. The resulting solution was subsequently dried at 60°C until the residue This temperature was maintained for 24 hours. At this operation stage, the moment of Rub, to Ru0t Decomposition was observed (black precipitate).

このようにして得られた乾燥残留物５０ηが水２５＃！ｅに懸濁され、懸濁物を まずアルゴンでガス抜きした後、照射した（キセノンランプｎｏ　４５０ワツト ）。50η of the dry residue thus obtained is 25# of water! e, the suspension is suspended in First, after degassing with argon, it was irradiated (xenon lamp no. 450 watts). ).

ヘキサクロロプラチネートアニオンの還元力、Ｊ、ＡｌＴｌ。Reducing power of hexachloroplatinate anion, J, AlTl.

Ｇｈｅｍ、　Ｓｏｃ、旦０　、４３１８（１９７８）　に説明された方法にした がって実施され、照射は約３０分後に、ガス相に水素が発生後たゾちに中止され た。Ghem, Soc, Dan0, 4318 (1978). The irradiation was then stopped after about 30 minutes, as soon as hydrogen was generated in the gas phase. Ta.

ｂ）触媒の増感（Ｔｉｅ、／Ｐｃ／Ｒｕｂ、　）ルテニウム錯塩（ＲｕＬ＆）Ｃ １，が３節で得られた触媒懸濁物（５０■）１こ添加された。添加砒は１．５Ｘ １０’物のｐＨ値はＨＣｌｊこより２に調整される。b) Catalyst sensitization (Tie, /Pc/Rub, ) Ruthenium complex salt (RuL&)C 1, was added to the catalyst suspension (50 cm) obtained in Section 3. Added arsenic is 1.5X The pH value of the 10' product is adjusted to 2 using HClj.

得られた懸濁物を入れた５０ゴの丸底フラスコが凝縮器付きの装置（こ接続され た。凝縮器は毛細管を経て水３０ａｃｅをふくむ第二番目の容器に接続され、シ ステム全体がアルゴンでガス抜きされた。懸濁物は引き続きかく拌しながら加熱 沸騰させ、紫外線フィルター（４２０ｎｍ）および循環水を収容した二重壁を備 えたキセノンランプ（ＸＢＯ４５Ｑワット）で照射された。A 50-gallon round-bottomed flask containing the resulting suspension was placed in a device with a condenser (this is connected to Ta. The condenser is connected via a capillary tube to a second container containing 30 ace of water, The entire stem was degassed with argon. The suspension is heated with continued stirring. Boiling, equipped with a double wall containing UV filter (420 nm) and circulating water. It was irradiated with a xenon lamp (XBO45Q Watt).

懸濁物の照射は沸点で２４時間継続され、増感された触媒の粒子が超遠心分離に より回収された。照射中、錯塩（ＲｕＬ３）（：Ｉ　２　が徐々に溶液から消失 し、この現象はＴｉＯβｔハｕＯ，粒子の濃厚な着色を伴なった。Irradiation of the suspension was continued for 24 hours at the boiling point, and the sensitized catalyst particles were subjected to ultracentrifugation. was recovered from. During irradiation, the complex salt (RuL3) (:I2) gradually disappears from the solution. However, this phenomenon was accompanied by intense coloring of the TiOβt particles.

得られた溶液はその紫外線吸収スペクトル（第１図参照〕を特徴とするものであ るが、この吸収スペクトルから４６６　ｎ　ｍ　（５％以下の濃度）における錯 塩（ＲｕＬすＣ１，の典型的な吸収をはゾ完全に消失したことが確認された。３ Ｑ５ｎｍにおける上記溶液の最大吸収率はジイソプロピル２．２’−ビピリジル −４゜４′−ジカルボキシレートの配位子に起因するものであった。The resulting solution is characterized by its ultraviolet absorption spectrum (see Figure 1). However, this absorption spectrum shows that the complex at 466 nm (concentration below 5%) It was confirmed that the typical absorption of the salt (RuL C1) completely disappeared.3 The maximum absorption of the above solution at Q5nm is diisopropyl 2,2'-bipyridyl This was attributed to the -4°4'-dicarboxylate ligand.

クロモフォールＲｕＬ２＋十の固定は、【（，０およびメタノールによる粒子の 連続洗浄でテストされた。Fixation of chromophor RuL2+ was carried out by [(,0 and Tested with continuous cleaning.

第二番目の実験で水４０　ｄ　（ｐＨ２）中でのＴｉＯβ【／Ｒｕ０ｔ触媒２５ Ｈｉの懸濁物の照射が１００℃で３６時間継続された。増感された触媒の粒子を 濾過、水洗。In the second experiment, TiOβ [/Ru0t catalyst 25 in water 40 d (pH 2) Irradiation of the Hi suspension was continued for 36 hours at 100°C. Sensitized catalyst particles Filtration and washing.

空気中で乾燥し、このように精製された触媒はその反射スペクトル（第２図）で 特徴付けられた。このスペクトルは４８（ｌｎｍで最大で終りが６００℃％ｍを 越えてのびる範囲の吸収率を特徴とする。この特徴的な吸収率は上述の通り、Ｔ ｉ０２粒子に化学的に結合されたクロモフォールＲｕ　Ｌｘ”に起因するもので あつた。The catalyst, dried in air and purified in this way, has a reflection spectrum (Figure 2) that shows characterized. This spectrum has a maximum of 48 (lnm) and ends at 600℃%m. It is characterized by an absorption rate that extends beyond. As mentioned above, this characteristic absorption rate is T This is caused by chromophor Ru　Lx'' chemically bonded to i02 particles. It was hot.

実施例２ 水の光還元に対する増感酸化／還元触媒の利用水中（ｐＨ１０）　にトリエタノ ールアミンをふくむ１０−２モル溶液５　ｙｔｅをＲｕＬ７”　で増感されたＴ ｉｅ２／Ｐｔ／Ｒｕ０ｔ触媒１１９の存在下で実施例１において説明した装置に より２５℃で照射した。キセノンランプＸＢＯ４５０’７　ツ）　（強度２００ 　ｍＷ／ｃＪ　）　Ｉｃ　、Ｊｌ、　ル４０５ｎｍ以上のλで照射。水素ガスが ０．９３ｍ／／ｈの割合で発生した。Example 2 Utilization of sensitized oxidation/reduction catalysts for photoreduction of water Trietano in water (pH 10) 5 yte of a 10-2 molar solution containing amine was sensitized with RuL7''. In the apparatus described in Example 1 in the presence of ie2/Pt/Ru0t catalyst 119 It was irradiated at 25°C. Xenon lamp XBO450'7) (Intensity 200 mW/cJ) Ic, Jl, Irradiation with λ of 405 nm or more. hydrogen gas It occurred at a rate of 0.93 m//h.

４６５０ｍの紫外線フィルターを利用すると、水素ガス収量の２０％低下が観察 された。５９０　ｎｍより大きいλで照射すると、水素ガスが５ｏμｌ／ｈの割 合で発生した。A 20% decrease in hydrogen gas yield was observed when using a 4650 m UV filter. It was done. When irradiated with λ larger than 590 nm, hydrogen gas is Occurred when

実施例３ 水の光分解に対する増感酸化／還元触媒の利用水（ｐＨ２）４０　ｍｌにＲｕＬ ｔ　で増感されりＴｉＯ２／／Ｉ）Ｌ／Ｒｕ０ｔ　触媒５０ηの懸濁液を実施例 １で説明した装置内で１００℃で照射した。λは４２００ｍ　Ｊｕ上である。水 素ガスは最初３０μｅ／ｈ　の割合で発生し、２０時間照射後は、４００μｅの 容積となった。Example 3 Use of sensitized oxidation/reduction catalyst for photolysis of water Add RuL to 40 ml of water (pH 2) An example of a suspension of TiO2//I)L/Ru0t catalyst 50η sensitized with t The irradiation was carried out at 100° C. in the apparatus described in 1. λ is above 4200 m Ju. water The elementary gas is initially generated at a rate of 30 μe/h, and after 20 hours of irradiation, it is generated at a rate of 400 μe/h. It became the volume.

照射中（１２時間後に４００μｌのサンプルを取り出す）ガスのクロマトグラフ 分析では、実質上化学量論的な比率でのガス状混合物は、Ｈ，２４０μｌ（±２ ０）および０２（±１０　）　１２０μｅで、残りは空気の存在による補正に起 因するものであることを示した。Gas chromatograph during irradiation (400 μl sample removed after 12 hours) In the analysis, the gaseous mixture in substantially stoichiometric proportions was mixed with H, 240 μl (±2 0) and 02 (±10) 120 μe, the rest is due to correction due to the presence of air. It was shown that this was caused by

増感された触媒が上述の条件下で、１００℃で２週間以上照射された後も液性を 示すことも観察された。The sensitized catalyst maintained its liquid properties even after being irradiated for more than two weeks at 100°C under the above conditions. It was also observed that

λ（ｎｍ） λ（ｎｍ１ 国際調査報告λ (nm) λ(nm1 international search report

Claims (10)

【特許請求の範囲】[Claims] １．ビピリジル若しくはフエナンスロイル型の配位子と遷移金属の錯塩フラグメ ントからなるクロモフオールをその表面に含む半導体系酸化／還元光反応触媒。1. Complex salt fragments of bipyridyl or phenanthroyl type ligands and transition metals A semiconductor-based oxidation/reduction photocatalyst containing chromophore on its surface. ２．チタン酸化物を基剤とし、クロモフオールがルテニウム，クローム若しくは 鉄錯塩のフラグメントから成ることを特徴とする請求範囲第１項に記載の半導体 系酸化／還元光反応触媒。2. Based on titanium oxide, chromophor is ruthenium, chromium or Semiconductor according to claim 1, characterized in that it consists of a fragment of an iron complex salt. System oxidation/reduction photoreaction catalyst. ３．上記クロモフオールが、一般式 ▲数式、化学式、表等があります▼ ただし、記号Ｌは配位子であるジイソプロピル２，２′−ビピリジル−４，４′ −ジカルボキシレート（Ｓｉｃ）を表わし、この錯塩フラグメントから成ること を特徴とする請求の範囲第１項又は第２項に記載の半導体系酸化／還元光反応触 媒。3. The above chromophor has the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ However, the symbol L is the ligand diisopropyl 2,2'-bipyridyl-4,4' - represents a dicarboxylate (Sic) and consists of a complex salt fragment thereof The semiconductor-based oxidation/reduction photocatalyst according to claim 1 or 2, characterized in that Medium. ４．その表面に、ビピリジル若しくはフエナンスロイル型の配位子と遷移金属と の錯塩のフラグメントからなるクロモフオールを固定させ、可視光線領域へ触媒 の光吸収帯をシフトさせることからなる半導体系酸化／還元光反応触媒の増感方 法。4. Bipyridyl- or phenanthroyl-type ligands and transition metals are present on the surface. Fixed chromophore consisting of a complex salt fragment of How to sensitize semiconductor-based oxidation/reduction photocatalysts by shifting the light absorption band of Law. ５．上記触媒が酸化チタンを基剤とし、クロモフオールがルテニウム，クローム あるいは鉄錯塩のフラグメントから成ることを特徴とする請求の範囲第４項に記 載の半導体系酸化／還元光反応触媒の増感方法。5. The above catalyst is based on titanium oxide, and the chromophore is ruthenium and chromium. Alternatively, the method according to claim 4 is characterized in that the iron complex salt is made of a fragment of an iron complex salt. A method for sensitizing semiconductor-based oxidation/reduction photoreaction catalysts. ６．上記クロモフオールが一般式 ▲数式、化学式、表等があります▼ ただし、記号Ｌは配位子であるジイソプロピル２，２′一ビピリジル−４，４′ −ジカルボキシレートを表わし、この錯塩のフラグメントから成ることを特徴と する請求の範囲第４項又は第５項に記載の半導体系酸化／還元光反応触媒の増感 方法。6. The above chromophor has the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ However, the symbol L is the ligand diisopropyl 2,2'-bipyridyl-4,4' - represents a dicarboxylate and is characterized by consisting of a fragment of this complex salt. Sensitization of the semiconductor-based oxidation/reduction photoreaction catalyst according to claim 4 or 5. Method. ７．光反応触媒が、一般式 ▲数式、化学式、表等があります▼ ただし、Ｌは請求の範囲第６項に規定されたものであり、Ｘはハロゲン原子を表 わし、この錯塩の酸性水溶液の存在下に照射されることを特徴とする請求の範囲 第６項に記載の半導体系酸化／還元光反応触媒の増感方法。7. The photoreaction catalyst has the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ However, L is defined in claim 6, and X represents a halogen atom. A claim characterized in that irradiation is performed in the presence of an acidic aqueous solution of this complex salt. 7. A method for sensitizing a semiconductor-based oxidation/reduction photoreaction catalyst according to item 6. ８．照射が５０℃と錯塩溶液の沸点との範囲内の温度で実施され、上記溶液のｐ Ｈ値が１乃至３の範囲にあることを特徴とする請求の範囲第７項に記載の半導体 系酸化／還元光反応触媒の増感方法。8. The irradiation is carried out at a temperature between 50° C. and the boiling point of the complex salt solution, and the p The semiconductor according to claim 7, characterized in that the H value is in the range of 1 to 3. Sensitization method for oxidation/reduction photocatalysts. ９．可視光線中で水性あるいは水性有機液体の光酸化に請求の範囲第１項乃至第 ３項のいずれかに記載の酸化／還元光反応触媒の利用。9. Claims 1 to 3 are applied to photooxidation of aqueous or aqueous organic liquids in visible light. Use of the oxidation/reduction photoreaction catalyst according to any of Item 3. １０．可視光線中で水性液体の光分解に請求の範囲第１項乃至第３項のいずれか に記載の酸化／還元光反応触媒の利用。10. Any one of claims 1 to 3 for photodecomposition of an aqueous liquid in visible light. Utilization of the oxidation/reduction photoreaction catalyst described in .
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